Search NASA⌕ Search

SEARCH · Search NASA

Results for “Cross-Link Ranging”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Direct Functionalization of Established 3D-Printed Aza-Michael Liquid Crystal Elastomers with Donor–Acceptor Stenhouse Adducts

Extrusion 3D printing has advanced the manufacturing of complex liquid crystal elastomer (LCE) architectures. In parallel, donor–acceptor Stenhouse adducts (DASAs), a class of white-light-responsive photoswitches, have enabled both photochemical and photothermal LCE actuation. However, DASA–LCEs have yet to be extruded and 3D-printed. Two key challenges exist: DASA’s inherent sensitivity to heat and radicals can lead to degradation during ink preparation and printing, and small changes in the concentration of the added DASA component impact the properties of the extrudable ink, requiring reoptimization of well-established 3D-printing protocols. To overcome these challenges, we present a post-printing functionalization strategy that circumvents these limitations. Residual secondary amines, inherent to inks synthesized via standard aza-Michael addition, serve as active sites for covalent attachment of DASA photoresponsive groups following printing and cross-linking. Our method means that DASAs can be directly grafted onto 3D-printed aza-Michael LCEs without modifying the ink formulation or processing. The resulting DASA–LCEs exhibit wavelength tunability within the visible range and a variety of photothermal and photochemical responses. The post-functionalization can occur within 2 min and enables spatial control of the DASA concentration, producing films with tunable color gradients and locally varied photothermal and photochemical responses under visible light. In conclusion, this approach enables the rapid fabrication of DASA-based light-responsive LCEs using established ink formulations with the potential for the design of complex 3D architectures.

3D printing↗

Highly Porous Polyimide Gel for Use as Battery Separator with Room Temperature Ionic Liquid Electrolytes

Advanced aerospace vehicular concepts require advances in many existing technologies, including space power and energy storage systems. Batteries represent one of the major areas in need of improvement, both in terms of energy density and safety, with growing concerns over the fire safety of commercial lithium-ion batteries. This has prompted efforts to develop nonflammable battery components, namely the electrolyte and separator. Existing commercial lithium-ion batteries utilize polyolefin microporous membranes as separators with an electrolyte consisting of a lithium salt dissolved in a mixture of cyclic carbonate solvents. This separator/electrolyte combination has ionic conductivities in the range of 10 −2 to 10 −3 S/cm. However, the cyclic carbonate solvents are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative. They offer good ionic conductivities and are inherently nonvolatile and nonflammable, giving them a safety advantage. However, many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Alternative separator materials, such as polyimides, are non-flammable and are capable of accepting RTILs into their structure. Polyimide gels, with a composition of 4,4′-oxydianiline, 3,3′,4,4′-tetracarboxylic dianhydride and cross-linked with Desmodur N3300A, possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85% porosity) for lithium-ion transport and conduction, as well as good mechanical properties. Furthermore, these polyimide gels are compatible with selected imidazolium-based RTILs. Nonflammable separator/electrolyte systems with room-temperature conductivities in the range of 10 −3 S/cm have been evaluated. It has been demonstrated that 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was the most promising among six RTILs screened, in terms of both ionic conductivity and constant current cycling.

Polyimide↗

Purification of the small mechanosensitive channel of Escherichia coli (MscS): the subunit structure, conduction, and gating characteristics in liposomes

The small mechanosensitive channel, MscS, is a part of the turgor-driven solute efflux system that protects bacteria from lysis in the event of osmotic downshift. It has been identified in Escherichia coli as a product of the orphan yggB gene, now called mscS (Levina et al., 1999, EMBO J. 18:1730). Here I show that that the isolated 31-kDa MscS protein is sufficient to form a functional mechanosensitive channel gated directly by tension in the lipid bilayer. MscS-6His complexes purified in the presence of octylglucoside and lipids migrate in a high-resolution gel-filtration column as particles of approximately 200 kDa. Consistent with that, the protein cross-linking patterns predict a hexamer. The channel reconstituted in soybean asolectin liposomes was activated by pressures of 20-60 mm Hg and displayed the same asymmetric I-V curve and slight anionic preference as in situ. At the same time, the single-channel conductance is proportional to the buffer conductivity in a wide range of salt concentrations. The rate of channel activation in response to increasing pressure gradient across the patch was slower than the rate of closure in response to decreasing steps of pressure gradient. Therefore, the open probability curves were recorded with descending series of pressures. Determination of the curvature of patches by video imaging permitted measurements of the channel activity as a function of membrane tension (gamma). Po(gamma) curves had the midpoint at 5.5 +/- 0.1 dyne/cm and gave estimates for the energy of opening DeltaG = 11.4 +/- 0.5 kT, and the transition-related area change DeltaA = 8.4 +/- 0.4 nm(2) when fitted with a two-state Boltzmann model. The correspondence between channel properties in the native and reconstituted systems is discussed.

NASA Discipline Cell Biology↗

Elasticity and Strength of Biomacromolecular Crystals: Lysozyme

The static Young modulus, E = 0.1 to 0.5 GPa, the crystal critical strength (sigma(sub c)) and its ratio to E,sigma(sub c)/E is approximately 10(exp 3), were measured for the first time for non cross-linked lysozyme crystals in solution. By using a triple point bending apparatus, we also demonstrated that the crystals were purely elastic. Softness of protein crystals built of hard macromolecules (26 GPa for lysozyme) is explained by the large size of the macromolecules as compared to the range of intermolecular forces and by the weakness of intermolecular bonds as compared to the peptide bond strength. The relatively large reported dynamic elastic moduli (approximately 8 GPa) from resonance light scattering should come from averaging over the moduli of intracrystalline water and intra- and intermolecular bonding.

Holmes, A. M.↗

Molecular Dynamics Simulation and Theoretical Analysis of Structural Relaxation, Bond Exchange Dynamics, and Glass Transition in Vitrimers

Vitrimers are a class of polymer networks featuring dynamic covalent cross-links that can undergo associative bond exchange. There has been recent interest in these materials due to their promise as recyclable thermosets or self-healing polymers because of the ability of vitrimer networks to rearrange at the molecular level and undergo macroscopic flow. However, the practical use of these materials often occurs in the supercooled regime or glassy state, where the implications of dynamic bonds are complicated by the interplay between slow activated segmental dynamics, cross-link (i.e., bond-exchange) kinetics, and ultimately material properties. Here, in this paper, we combine coarse-grained molecular dynamics simulation and microscopic statistical mechanical theory to understand how cross-linking kinetics affect material dynamics and how this couples to segmental relaxation of the polymeric network strands across a spectrum of length and time scales, especially in the supercooled regime. We characterize the Kuhn segmental alpha relaxation time and bond exchange time for vitrimer systems across various cross-link densities, temperatures, and bond exchange rates. Simulation and theory both exhibit a bending-up behavior for bond exchange time upon cooling, suggesting a coupling between bond exchange dynamics and segmental relaxation that intensifies with faster bond exchange kinetics. We also found bond exchange dynamics have an impact on Kuhn segment alpha relaxation time, which is most significant at higher cross-link densities. Both these effects are most prominent when the bond exchange time is similar to the Kuhn segment alpha relaxation time, and the resulting coupling of these two relaxation processes is tied to both the probability of a free end to find a bonded pair and the time scale of the constraints imposed by the dynamic cross-links. This relationship is reflected by a cross-link dependence of a theoretical parameter which represents the quantitative degree of coupling between bond exchange and segmental dynamics. Overall, the combination of simulation and theory clarifies the intricate interaction between bond kinetics and segmental relaxation and demonstrates the ability to provide molecular-level insights into vitrimer dynamics over a wide temperature range.

dynamic relaxation↗

Fuel decomposition and boundary-layer combustion processes of hybrid rocket motors

Using a high-pressure, two-dimensional hybrid motor, an experimental investigation was conducted on fundamental processes involved in hybrid rocket combustion. HTPB (Hydroxyl-terminated Polybutadiene) fuel cross-linked with diisocyanate was burned with GOX under various operating conditions. Large-amplitude pressure oscillations were encountered in earlier test runs. After identifying the source of instability and decoupling the GOX feed-line system and combustion chamber, the pressure oscillations were drastically reduced from +/-20% of the localized mean pressure to an acceptable range of +/-1.5% Embedded fine-wire thermocouples indicated that the surface temperature of the burning fuel was around 1000 K depending upon axial locations and operating conditions. Also, except near the leading-edge region, the subsurface thermal wave profiles in the upstream locations are thicker than those in the downstream locations since the solid-fuel regression rate, in general, increases with distance along the fuel slab. The recovered solid fuel slabs in the laminar portion of the boundary layer exhibited smooth surfaces, indicating the existence of a liquid melt layer on the burning fuel surface in the upstream region. After the transition section, which displayed distinct transverse striations, the surface roughness pattern became quite random and very pronounced in the downstream turbulent boundary-layer region. Both real-time X-ray radiography and ultrasonic pulse-echo techniques were used to determine the instantaneous web thickness burned and instantaneous solid-fuel regression rates over certain portions of the fuel slabs. Globally averaged and axially dependent but time-averaged regression rates were also obtained and presented.

Chiaverini, Martin J.↗

Combustion of solid fuel slabs with gaseous oxygen in a hybrid motor analog

Using a high-pressure, two-dimensional hybrid motor, an experimental investigation was conducted on fundamental processes involved in hybrid rocket combustion. HTPB (Hydroxyl-terminated Polybutadiene) fuel cross-linked with diisocyanate was burned with gaseous oxygen (GOX) under various operating conditions. Large-amplitude pressure oscillations were encountered in earlier test runs. After identifying the source of instability and decoupling the GOX feed-line system and combustion chamber, the pressure oscillations were drastically reduced from plus or minus 20% of the localized mean pressure to an acceptable range of plus or minus 1.5%. Embedded fine--wire thermocouples indicated that the surface temperature of the burning fuel was around 1000 K depending upon axial locations and operating conditions. Also, except near the leading edge region, the subsurface thermal wave profiles in the upstream locations are thicker than those in the downstream locations since the solid-fuel regression rate, in general, increases with distance along the fuel slab. The recovered solid fuel slabs in the laminar portion of the boundary layer exhibited smooth surfaces, indicating the existence of a liquid melt layer on the burning fuel surface in the upstream region. After the transition section, which displayed distinct transverse striations, the surface roughness pattern became quite random and very pronounced in the downstream turbulent boundary-layer region. Both real-time X-ray radiography and ultrasonic pulse echo techniques were used to determine the instantaneous web thicknesses and instantaneous solid-fuel regression rates over certain portions of the fuel slabs. Globally averaged and axially dependent but time-averaged regression rates were also obtained and presented. Several tests were conducted using, simultaneously, one translucent fuel slab and one fuel slab processed with carbon black powder. The addition of carbon black did not affect the measured regression rates or surface temperatures in comparison to the translucent fuel slabs.

Chiaverini, Martin J.↗

Creation of Self-Semi-Interpenetrating Network Structures in PIM-1 Membranes for Enhanced Physical Aging Resistance

A series of self-semi-interpenetrating network (ssIPN) thin films based on PIM-1 structure were developed by end-cross-linking telechelic PIM-1 oligomers end-capped with curable carboxylic acid groups to form model networks, which are penetrated by linear high-molecular-weight PIM-1 chains. ssIPN films with systematically varied network content ranging from 10 to 30 wt % were comprehensively examined on their microstructure and gas permeation properties. Fresh PIM-1 ssIPN films exhibited gas separation performances close to those of as-cast linear PIM-1, where the films closely followed the upper bound trade-off line, gaining as much selectivity as they lose gas permeability as the network content increases. This indicates that gas permeability is largely preserved despite cross-linking. Wide-angle X-ray scattering supported this observation, with peaks shifting toward lower d-spacing as oligomer content increased, suggesting tighter chain packing with higher cross-linkable oligomer loading. In physical aging studies over two months, all ssIPN films outperform linear PIM-1 for H 2 /CH 4 and O 2 /N 2 separations. Notably, the PIM-1 ssIPN with 10 wt % network content showed the best physical aging resistance, with negligible permeability loss even after one month. Finally, these findings highlight a promising macromolecular strategy for enhancing the physical aging resistance of microporous polymer membranes for gas separation.

PIM-1↗

In Situ Analysis of Electron-Induced Chemical Transformations in Vapor-Phase-Synthesized Al-Based Inorganic–Organic Hybrid Thin Films for EUV Resist Platform

The rapid advancement and stringent requirements of extreme ultraviolet (EUV) lithography technology necessitate the development of advanced photoresist systems for next-generation microelectronics. Recent studies have demonstrated that inorganic-based hybrid photoresists offer notable improvements in EUV sensitivity, etch resistance, and greater insusceptibility to pattern collapse compared to their purely organic counterparts. However, variations in the synthesis/coating approaches and chemistry of inorganic–organic photoresists can result in distinct exposure mechanisms. In this work, an Al-based hybrid thin film resist system synthesized via molecular (atomic) layer deposition (MLD or MALD) is explored, focusing on its electron-beam and EUV patterning mechanisms. The Al-based hybrid thin films are deposited using trimethylaluminum (TMA) and the organic precursor hydroquinone, exhibiting a saturated growth rate within the temperature range of 150–200°C. In diluted tetramethylammonium hydroxide (TMAH)-based developer solutions, the electron-irradiated Al-based hybrid thin film system behaves as a negative tone resist, achieving a sensitivity of 10.4 mC/cm 2 at 0.1 kV electron beam lithography (EBL). Chemical changes induced by electron exposure are also analyzed in this study using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and a unique infrared spectroscopy setup, revealing the potential cross-linking pathways. To further correlate the electron-induced chemical transformations with those mediated by EUV irradiations, a combination of X-ray photoemission electron microscopy/low-energy electron microscopy (XPEEM/LEEM) system is also employed. In conclusion, this study provides critical insights into the mechanisms underlying solubility switching and contributes to the design of advanced resist materials for EUV lithography.

36 MATERIALS SCIENCE↗

Synthesis and Characterization of Methacrylamide-Based Block Random Copolymers via Amine Functionalization of Polystyrene- Block -Poly(Pentafluorophenyl Methacrylate) Toward Enhanced Amenability to Manufacturing Criteria in Nanolithography

Recent interest in manipulating the chemistry of block copolymers (BCPs) to manage the covarying properties necessary to meet manufacturing criteria in nanolithography has resulted in the development and expansion of the A-block-(B-random-C) BCP architecture, where the random block allows for the decoupling of thermodynamic and wetting properties. Previous reports of such BCPs have used click chemistry to create the desired random block, but all such instances possess additional functional groups that are susceptible to undesirable side reactions upon annealing, such as cross-linking and surface grafting. This study reports the substitution reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with primary amines. The resulting methacrylamide structure of the functionalized random block has only an amide linkage between the attached functional group and the polymer backbone, thereby omitting any sources of side reactions within the BCP. The outcomes of this report also demonstrate the enhanced thermal stability of these materials by virtue of their stable amide bonds. A range of random copolymer compositions is assessed to develop BCPs in which the random block has approximately the same surface energy as the PS block. These BCPs can self-assemble into perpendicular lamellae and are therefore promising candidates for directed self-assembly.

block copolymers↗

A Sensitive Electrochemical Cholinesterase-Inhibiting Biosensor for Organophosphorus Pesticides Based on Ti 3 C 2 TX MXene Quantum Dots

Organophosphorus pesticides (OPs) pose significant environmental and health risks due to their widespread use and toxicity, primarily by inhibiting acetylcholinesterase. Traditional detection methods are often slow and costly, highlighting the urgent need for advanced, sensitive, and accessible technologies. This study developed a highly sensitive electrochemical cholinesterase-inhibiting biosensor for OP pesticides, utilizing Ti 3 C 2 T x MXene Quantum Dots (MQDs), which was synthesized via a hydrothermal method. The biosensor’s performance was characterized using electrochemical impedance spectroscopy, differential pulse voltammetry (DPV), and cyclic voltammetry. DPV proved to be the optimal technique, exhibiting an ultralow detection limit of 1 × 10 −17 M and a wide linear range (10 −14 –10 −8 M) for chlorpyrifos (a model OP) with an estimated inhibition constant of 62 nM. The biosensor demonstrated high selectivity for OPs (chlorpyrifos, acephate, glyphosate) over a non-target pyrethroid (permethrin), confirmed by distinct electrochemical signatures and compared to in vitro cholinergic activity assays in bean beetle homogenates. The enhanced performance is attributed to the high surface-to-volume ratio, quantum confinement effects, and superior conductivity of the MQDs, as well as the robust enzyme immobilization facilitated by glutaraldehyde cross-linking and a chitosan matrix. This work presents a promising platform for rapid, sensitive, and selective detection of OP pesticides, with potential applications in environmental monitoring and public health protection.

Chemistry↗

Status of high temperature adhesives

The status of high temperature organic adhesives is reviewed. These materials are defined by having usable adhesive properties at temperatures ranging from 232 C (after hundreds of hours at 232 C) to 538 C (after a few minutes at 538 C). The search for high temperature adhesives began in the 1960s, primarily under government funding. Since then, many high temperature polymers have undergone evaluation as adhesives. In spite of this effort, only a few are commercially available because of an elusive market and an unfavorable combination of price, processability and performance. The principal adhesives to be discussed will be addition and condensation polyimides, polyquinoxalines, polybenzimidazoles, and addition, condensation, and cross-linked polyphenylquinoxalines. The synthesis, processability, adhesive performance, and availabiity of these materials are addressed.

Hergenrother, P. M.↗

Chain Dynamics in Magnetorheological Suspensions

Magnetorheological (MR) suspensions are composed of colloidal particles which acquire dipole moments when subjected to an external magnetic field. At sufficient field strengths and concentrations, the dipolar particles rapidly aggregate to form long chains. Subsequent lateral cross-linking of the dipolar chains is responsible for a rapid liquid-to-solid-like rheological transition. The unique, magnetically-activated rheological properties of MR suspensions make them ideal for interfacing mechanical systems to electronic controls. Additionally, the ability to experimentally probe colloidal suspensions interacting through tunable anisotropic potentials is of fundamental interest. Our current experimental work has focused on understanding the fluctuations of dipolar chains. It has been proposed by Halsey and Toor (HT) that the strong Landau-Peierls thermal fluctuations of dipolar chains could be responsible for long-range attractions between chains. Such interactions will govern the long-time relaxation of MR suspensions. We have synthesized monodisperse neutrally buoyant MR suspensions by density matching stabilized ferrofluid emulsion droplets with D2O. This allows us to probe the dynamics of the dipolar chains using light scattering without gravitational, interfacial, and polydispersity effects to resolve the short-wavelength dynamics of the dipolar chains. We used diffusing wave spectroscopy to measure these dynamics. The particle displacements at short times that show an independence to the field strength, but at long times exhibit a constrained, sub-diffusive motion that slows as the dipole strength is increased. The experiments are in good qualitative agreement with Brownian dynamics simulations of dipolar chains. Although there have been several important and detailed studies of the structure and interactions in MR suspensions, there has not been conclusive evidence that supports or contradicts the HT model prediction that long-range interactions exist between fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead-spring systems. These chains form the basis for our current experiments with optical traps.

Gast, A. P.↗

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Synthetic polymers have found widespread use, but their ineffective end-of-life treatment is causing a significant environmental and human health crisis. Here, we demonstrate the upcycling of polynorbornene derivatives (pNBEs) through their deconstruction into distinct oligomeric buildings blocks that can be repolymerized into chemically recyclable pNBEs-like multiblock polymers via dehydrogenative polymerization. The resulting materials exhibit diverse mechanical properties, while integrating high melting temperatures (T m as high as 133 °C). Notably, this method could also enable the selective deconstruction of permanently cross-linked polydicyclopentadiene (pDCPD) thermosets into telechelic-OH functionalized oligomers, overcoming the significant challenges posed by their robust network structure in recycling and degradation. The resulting pDCPD oligomers can subsequently be repolymerized with macrodiols to create multiblock thermosets with tunable mechanical properties, including Young's modulus and tensile elongation. After use, upcycled plastics could be effectively deconstructed back to the oligomers for recovery and repolymerization. Overall, this work establishes an approach that can be utilized to upcycle pNBEs into previously inaccessible multiblock thermosets and thermoplastics with full recyclability, and may be generalizable to a range of polymers to shift their end-of-life waste disposal toward sustainable recovery and reuse.

36 MATERIALS SCIENCE↗

A Hardware-in-the-Loop Testbed for Spacecraft Formation Flying Applications

The Formation Flying Test Bed (FFTB) at NASA Goddard Space Flight Center (GSFC) is being developed as a modular, hybrid dynamic simulation facility employed for end-to-end guidance, navigation, and control (GN&C) analysis and design for formation flying clusters and constellations of satellites. The FFTB will support critical hardware and software technology development to enable current and future missions for NASA, other government agencies, and external customers for a wide range of missions, particularly those involving distributed spacecraft operations. The initial capabilities of the FFTB are based upon an integration of high fidelity hardware and software simulation, emulation, and test platforms developed at GSFC in recent years; including a high-fidelity GPS simulator which has been a fundamental component of the Guidance, Navigation, and Control Center's GPS Test Facility. The FFTB will be continuously evolving over the next several years from a too[ with initial capabilities in GPS navigation hardware/software- in-the- loop analysis and closed loop GPS-based orbit control algorithm assessment to one with cross-link communications and relative navigation analysis and simulation capability. Eventually the FFT13 will provide full capability to support all aspects of multi-sensor, absolute and relative position determination and control, in all (attitude and orbit) degrees of freedom, as well as information management for satellite clusters and constellations. In this paper we focus on the architecture for the FFT13 as a general GN&C analysis environment for the spacecraft formation flying community inside and outside of NASA GSFC and we briefly reference some current and future activities which will drive the requirements and development.

Leitner, Jesse↗

Polymer-Oxygen Compatibility Testing: Effect of Oxygen Aging on Ignition and Combustion Properties

The oxygen compatibility of six polymers used in oxygen service was evaluated after exposure for 48 hours to oxygen pressures ranging from 350 to 6200 kPa (50 to 900 psia), and temperatures ranging from 50 to 250 C (122 to 302 F). Three elastomers were tested: CR rubber (C873-70), FKM fluorocarbon rubber (Viton A), and MPQ silicone rubber (MIL-ZZ-765, Class 2); and three thermoplastics were tested: polyhexamethylene adipamide (Zytel 42), polytetrafluoroethylene (Teflon TFE), and polychlorotrifluoroethylene (Neoflon CTFE M400H). Post-aging changes in mass, dimensions, tensile strength, elongation at break, and durometer hardness were determined. Also, the compression set was determined for the three elastomers. Results show that the properties under investigation were more sensitive to oxygen pressure at low to moderate temperatures, and more sensitive to temperature at low to moderate oxygen pressures. Inspection of the results also suggested that both chain scissioning and cross-linking processes were operative, consistent with heterogeneous oxidation. Attempts are underway to verify conclusively the occurrence of heterogeneous oxidation using a simple modulus profiling technique. Finally, the effect of aging at 620 kpa (90 psia) and 121 C (250 F) on ignition and combustion resistance was determined. As expected, aged polymers were less ignitable and combustible (had higher AlTs and lower heats of combustion). Special attention was given to Neoflon CTFE. More specifically, the effect of process history (compression versus extrusion molding) and percent crystallinity (quick- versus slow-quenched) on the AIT, heat of combustion, and impact sensitivity of Neoflon CTFE was investigated. Results show the AIT, heat of combustion, and impact sensitivity to be essentially independent of Neoflon CTFE process history and structure.

Waller, Jess M.↗

Mechanically Strong, Polymer Cross-linked Aerogels (X-Aerogels)

Aerogels comprise a class of low-density, high porous solid objects consisting of dimensionally quasi-stable self-supported three-dimensional assemblies of nanoparticles. Aerogels are pursued because of properties above and beyond those of the individual nanoparticles, including low thermal conductivity, low dielectric constant and high acoustic impedance. Possible applications include thermal and vibration insulation, dielectrics for fast electronics, and hosting of functional guests for a wide variety of optical, chemical and electronic applications. Aerogels, however, are extremely fragile materials, hence they have found only limited application in some very specialized environments, for example as Cerenkov radiation detectors in certain types of nuclear reactors, aboard spacecraft as collectors of hypervelocity particles (refer to NASA's Stardust program) and as thermal insulators on planetary vehicles on Mars (refer to Sojourner Rover in 1997 and Spirit and Opportunity in 2004). Along these lines, the X-Aerogel is a new NASA-developed strong lightweight material that has resolved the fragility problem of traditional (native) aerogels. X-Aerogels are made by applying a conformal polymer coating on the surfaces of the skeletal nanoparticles of native aerogels (see Scanning Electron Micrographs). Since the relative amounts of the polymeric crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by the templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by remplated casting of polymer on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralighweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the the thermal conductivity of styrofoam. X-Aerogels have been demonstrated with several polymers such as polyurethanes/polyureas, epoxies and polyolefins, while crosslinking of approximately 35 different oxide aerogels yields a range of dimensionally stable, porous lightweight materials with unique combinations of structural, magnetic and optical properties. The main theme in materials development for space exploration is multifunction. For example, use of one material for thermal insulation/structural component will free weight for useful payload. In that regard, X-aerogels are evaluated at NASA for cryogenic fuel storage tanks and for spacesuits. Along the same lines, major impact fro X-Aerogels is also expected in commercial applications for thermal/acoustic insulation, in catalytic reformers and converters, in filtration membranes and membranes for fuel cells, as platforms for optical, electrical and magnetic sensors, and as lightweight structural component for aircraft and satellites.

Leventis, Nicholas↗

Fuel-rich catalytic combustion of a high density fuel

Fuel-rich catalytic combustion (ER is greater than 4) of the high density fuel exo-tetrahydrocyclopentadiene (JP-10) was studied over the equivalence ratio range 5.0 to 7.6, which yielded combustion temperatures of 1220 to 1120 K. The process produced soot-free gaseous products similar to those obtained with iso-octane and jet-A in previous studies. The measured combustion temperature agreed well with that calculated assuming soot was not a combustion product. The process raised the effective hydrogen/carbon (H/C) ratio from 1.6 to over 2.0, thus significantly improving the combustion properties of the fuel. At an equivalence ratio near 5.0, about 80 percent of the initial fuel carbon was in light gaseous products and about 20 percent in larger condensable molecules. Fuel-rich catalytic combustion has now been studied for three fuels with H/C ratios of 2.25 (iso-octane), 1.92 (jet-A), and 1.6 (JP-10). A comparison of the product distribution of these fuels shows that, in general, the measured concentrations of the combustion products were monotonic functions of the H/C ratio with the exception of hydrogen and ethylene. In these cases, data for JP-10 fell between iso-octane and jet-A rather than beyond jet-A. It is suggested that the ring cross-linking structure of JP-10 may be responsible for this behavior. All the fuels studied showed that the largest amounts of small hydrocarbon molecules and the smallest amounts of large condensable molecules occurred at the lower equivalence ratios. This corresponds to the highest combustion temperatures used in these studies. Although higher temperatures may improve this mix, the temperature is limited. First, the life of the present catalyst would be greatly shortened when operated at temperatures of 1300 K or greater. Second, fuel-rich catalytic combustion does not produce soot because the combustion temperatures used in the experiments were well below the threshold temperature (1350 K) for the formation of soot. Increasing the temperature above this value would remove the soot-free nature of the process. Since all the fuels studied show a similar breakdown of the primary fuel into smaller molecular combustion products, this technique can be applied to all hydrocarbon fuels.

Brabbs, Theodore A.↗